Compounds, compositions and uses

ABSTRACT

A compound of Formula (1) and salts thereof: wherein: M is 2H, Si, a metal, an oxymetal group, a hydroxymetal group or a halometal group; Pc represents a phthalocyanine nucleus of Formula (2); R 1 , R 2  and R 3  independently are H or optionally substituted C 1-4  alkyl; R 4  is an optionally substituted cyclic or an optionally substituted acyclic alkene optionally interrupted with a hetero atom; x and z are both greater than 0; y is 0 to 4; and the sum of (x+y+z) is 2 to 5. Also compositions and inks comprising compounds of Formula (1); processes for printing these compositions and substrates printed with said compositions and inks; and ink jet printer cartridges.

This invention relates to compounds, to compositions containing thesecompounds, to inks, to printing processes, to printed substrates and toink-jet printer cartridges.

Ink-jet printing is a non-impact printing technique in which droplets ofink are ejected through a fine nozzle onto a substrate without bringingthe nozzle into contact with the substrate.

There are many demanding performance requirements for dyes and inks usedin ink-jet printing. For example they desirably provide sharp,non-feathered images having good water light and ozone fastness andoptical density. The inks are often required to dry quickly when appliedto a substrate to prevent smudging, but they should not form a crustover the tip of an ink-jet nozzle because this will stop the printerfrom working. The inks should also be stable to storage over timewithout decomposing or forming a precipitate that could block the finenozzle. Dyes containing a single copper phthalocyanine group and theiruse in ink-jet printing are known. For example, C.I. Direct Blue 199 andC.I. Direct Blue 86 are used as colorants in commercial ink-jet printinginks.

A particular problem for photorealistic quality printing is that oflight-fastness. Prints are often exposed to daylight for long periodsand there is a need for the image to have as good light-fastness aspossible. The colorants in the print reacting with atmospheric ozone canplay a major role in poor light-fastness.

According to the present invention there is provided a compound ofFormula (1) and salts thereof:

wherein:

-   -   M is 2H, Si, a metal, an oxymetal group, a hydroxymetal group or        a halometal group;    -   Pc represents a phthalocyanine nucleus of Formula (2);    -   R¹, R² and R³ independently are H or optionally substituted        C₁₋₄alkyl;    -   R⁴ is an optionally substituted cyclic or an optionally        substituted acyclic alkene, optionally interrupted with a hetero        atom;    -   x and z are both greater than 0;    -   y is 0 to 4; and    -   the sum of (x+y+z) is 2 to 5.    -   M is preferably 2Li, 2Na, 2K, Mg, Ca, Ba, Al, Si, Sn, Pb, Rh,        Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, AlX, GaX, InX or SiX₂,        where in X is OH or Cl, more preferably Sc, Ti, Va, Cr, Mn, Fe,        Co, Zn, Ni and Cu and especially Cu or Ni.

Preferably R¹, R² and R³ independently are H or methyl.

Preferably R¹ and R² are both H.

In one preferred embodiment R⁴ is optionally substituted C₂₋₁₈ straightor branched chain alkylene or more preferably R⁴ is optionallysubstituted C₂₋₁₂ straight or branched chain alkylene it is especiallypreferred that R⁴ is optionally substituted C₃₋₆ straight chainalkylene.

In another preferred embodiment R⁴ is an optionally substituted C₂₋₁₈straight or branched chain alkylene interrupted with NH. In thisembodiment R⁴ is more preferably (CH₂)_(n)NH(CH₂)_(p)CH═CH(CH₂)_(q)Hwherein n is 1 to 3, and p and q are each independently 0 or 1.

Preferred optional substituents which may be present on R¹, R², R³ andR⁴ are selected from: alkoxy, preferably C₁₋₄-alkoxy; polyalkyleneoxide; nitro; cyano; sulpho; halo, especially bromo, chloro or fluoro;ureido; SO₂F; hydroxy; ester, more preferably —CO₂(C₁₋₄-alkyl); and—NR⁵R⁶, —COR⁵, —CONR⁵R⁶ and —SO₂NR⁵R⁶ wherein R⁵ and R⁶ are eachindependently H or alkyl, preferably H or C₁₋₄-alkyl. Optionalsubstituents for any of the substituents described for R¹, R², R³ and R⁴may be selected from the same list of substituents.

Preferably x is 0.2 to 3.8, more preferably 0.5 to 3.5, especially 1 to3 and more especially 1 to 2.

Preferably y is 0.2 to 3.8, more preferably 0.5 to 3.5, especially 1 to3 and more especially 1 to 2.

Preferably z is 0.2 to 3.8, more preferably 0.5 to 3.5, especially 1 to3 and more especially 1 to 2.

The sum of (x+y+z) is preferably 2 to 4, more preferably 3 to 4.

Acid or basic groups on the compounds of Formula (1), particularly acidgroups, are preferably in the form of a salt. Thus, the Formulae shownherein include the compounds in free acid and in salt form.

Preferred salts are alkali metal salts, especially lithium, sodium andpotassium, ammonium and substituted ammonium salts (including quaternaryamines such as ((CH₃)₄N⁺) and mixtures thereof. Especially preferred aresalts with sodium, lithium, ammonia and volatile amines, more especiallysodium salts. The compounds may be converted into a salt using knowntechniques.

The compounds of Formula (1) may exist in tautomeric forms other thanthose shown in this specification. These tautomers are included withinthe scope of the present invention.

The compounds of Formula (1) have attractive, strong cyan shades and arevaluable colorants for use in the preparation of ink-jet printing inks.They benefit from a good balance of solubility, storage stability andfastness to water and light. In particular they display excellent lightand ozone fastness. Furthermore they may be prepared from cheapintermediates, avoiding the complexity and expense which is involved inmanufacturing some of the more elaborate phthalocyanines.

According to a second aspect of the present invention there is provideda composition comprising a compound according to the first aspect of theinvention and a medium, preferably a liquid medium.

Preferred compositions comprise:

-   -   (a) from 0.01 to 30 parts of a compound according to the first        aspect of the invention; and    -   (b) from 70 to 99.99 parts of a liquid medium;        wherein all parts are by weight and the number of parts of        (a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. The numberof parts of component (b) is preferably from 99.9 to 80, more preferablyfrom 99.5 to 85, especially from 99 to 95 parts.

Preferably component (a) is completely dissolved in component (b).Preferably component (a) has a solubility in component (b) at 20° C. ofat least 10%. This allows the preparation of liquid dye concentratesthat may be used to prepare more dilute inks and reduces the chance ofthe dye precipitating if evaporation of the liquid medium occurs duringstorage.

Preferred liquid media include water, a mixture of water and organicsolvent or organic solvent free from water.

When the medium comprises a mixture of water and organic solvent, theweight ratio of water to organic solvent is preferably from 99:1 to1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to80:20.

It is preferred that the organic solvent present in the mixture of waterand organic solvent is a water-miscible organic solvent or a mixture ofsuch solvents. Preferred water-miscible organic solvents includeC₁₋₆-alkanols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol andcyclohexanol; linear amides, preferably dimethylformamide ordimethylacetamide; ketones and ketone-alcohols, preferably acetone,methyl ether ketone, cyclohexanone and diacetone alcohol; water-miscibleethers, preferably tetrahydrofuran and dioxane; diols, preferably diolshaving from 2 to 12 carbon atoms, for example pentane-1,5-diol, ethyleneglycol, propylene glycol, butylene glycol, pentylene glycol, hexyleneglycol and thiodiglycol and oligo- and poly-alkyleneglycols, preferablydiethylene glycol, triethylene glycol, polyethylene glycol andpolypropylene glycol; triols, preferably glycerol and 1,2,6-hexanetriol;mono-C₁₋₄-alkyl ethers of diols, preferably mono-C₁₋₄-alkyl ethers ofdiols having 2 to 12 carbon atoms, especially 2-methoxyethanol,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)-ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and ethyleneglycol monoallylether;cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and 1,3-dimethylimidazolidone; cyclicesters, preferably caprolactone; sulphoxides, preferably dimethylsulphoxide and sulpholane. Preferably the liquid medium comprises waterand 2 or more, especially from 2 to 8, water-miscible organic solvents.

Especially preferred water-miscible organic solvents are cyclic amides,especially 2-pyrrolidone, N-methyl-pyrrolidone and N-ethyl-pyrrolidone;diols, especially 1,5-pentane diol, ethyleneglycol, thiodiglycol,diethyleneglycol and triethyleneglycol; and mono-C₁₋₄-alkyl andC₁₋₄-alkyl ethers of diols, more preferably mono-C₁₋₄-alkyl ethers ofdiols having 2 to 12 carbon atoms, especially2-methoxy-2-ethoxy-2-ethoxyethanol.

Examples of further suitable liquid media comprising a mixture of waterand one or more organic solvents are described in U.S. Pat. No.4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP4,251,50A.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 300 to 200° C., more preferably of from 400 to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents are any of thehereinbefore-described water-miscible organic solvents and mixturesthereof. Preferred water-immiscible solvents include, for example,aliphatic hydrocarbons; esters, preferably ethyl acetate; chlorinatedhydrocarbons, preferably CH₂Cl₂; and ethers, preferably diethyl ether;and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably a polar solvent is included because this enhances solubilityof the compound in the liquid medium. Examples of polar solvents includeC₁₋₄-alcohols.

In view of the foregoing preferences it is especially preferred thatwhere the liquid medium is an organic solvent free from water itcomprises a ketone (especially methyl ethyl ketone) &/or an alcohol(especially a C₁₋₄-alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected thatgives good control over the drying characteristics and storage stabilityof the ink.

Liquid media comprising an organic solvent free from water areparticularly useful where fast drying times are required andparticularly when printing onto hydrophobic and non-absorbentsubstrates, for example plastics, metal and glass.

The liquid media may also contain additional components conventionallyused in ink jet printing inks, for example viscosity and surface tensionmodifiers, corrosion inhibitors, biocides, kogation reducing additivesand surfactants which may be ionic or non-ionic.

Although not usually necessary, further colorants may be added to thecomposition to modify the shade and performance properties. Examples ofsuch colorants include C.I.Direct Yellow 86, 132, 142 and 173;C.I.Direct Blue 199, and 307; C.I.Food Black 2; C.I.Direct Black 168 and195; C.I.Acid Yellow 23; and any of the dyes used in ink jet printerssold by Seiko Epson Corporation, Hewlett Packard Company, Canon Inc. &Lexmark International. Addition of such further dyes can increaseoverall solubility leading to less kogation (nozzle blockage) for theresultant ink.

It is preferred that the composition according to the second aspect ofthe invention is an ink suitable for use in an ink jet printer.

Thus, preferably the ink has a viscosity of less than 20 cP, morepreferably less than 10 cP, especially less than 5 cP, at 25° C. Theselow viscosity inks are particularly well suited for application tosubstrates by means of ink jet printers.

Preferably the ink contains less than 500 ppm, more preferably less than250 ppm, especially less than 100 μm, more especially less than 10 ppmin total of divalent and trivalent metal ions (other than any divalentand trivalent metal ions bound to a component of the ink).

Preferably the ink has been filtered through a filter having a mean poresize below 10 μm, more preferably below 3 μm, especially below 2 μm,more especially below 1 μm. This filtration removes particulate matterthat could otherwise block the fine nozzles found in many ink-jetprinters.

Preferably the ink contains less than 500 ppm, more preferably less than250 ppm, especially less than 100 pm, more especially less than 10 ppmin total of halide ions.

A third aspect of the invention provides a process for forming an imageon a substrate comprising applying an ink according to the second aspectof the invention thereto by means of an ink jet printer.

The ink-jet printer preferably applies the ink to the substrate in theform of droplets that are ejected through a small orifice onto thesubstrate. Preferred ink-jet printers are piezoelectric ink-jet printersand thermal ink-jet printers. In thermal ink-jet printers, programmedpulses of heat are applied to the ink in a reservoir by means of aresistor adjacent to the orifice, thereby causing the ink to be ejectedfrom the orifice in the form of small droplets directed towards thesubstrate during relative movement between the substrate and theorifice. In piezoelectric ink-jet printers the oscillation of a smallcrystal causes ejection of the ink from the orifice. Alternately the inkcan be ejected by an electromechanical actuator connected to a moveablepaddle or plunger, for example as described in International PatentApplication 00/48938 and International Patent Application 00/55089.

The substrate is preferably paper, plastic, a textile, metal or glass,more preferably paper, an overhead projector slide or a textilematerial, especially paper.

Preferred papers are plain or treated papers which may have an acid,alkaline or neutral character.

A fourth aspect of the present invention provides paper, plastic, atextile, metal or glass, more preferably paper, an overhead projectorslide or a textile material, especially paper more especially plain,coated or treated papers printed with a composition according to thesecond aspect of the invention, a compound according to the first aspectof the invention or by means of a process according to third aspect ofthe invention.

A fifth aspect of the present invention provides an ink jet printercartridge comprising a chamber and an ink wherein the ink is in thechamber and the ink is as described in the second aspect of the presentinvention.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

Preparation of:

Stage 1

Chlorosulphonic acid (38.5 ml, 0.57 mole) was charged to a 250 ml4-necked round-bottomed flask. POCl₃ (2.3 ml, 0.057 mole) was addeddropwise with continuous mixing over 10-15 minutes while maintaining thetemperature below 30° C. The reaction mixture was then stirred for afurther 10 minutes. Copper phthalocyanine (14.4 g, 10.025 mole) (CuPc)was added portion wise, with stirring, over approximately 45 minuteswhile maintaining the temperature below 55° C. After this addition wascomplete the reaction mixture was stirred for a further 45 minutes andthen warmed to 140±2° C. over approximately 20 minutes. The reactionmixture was held at this temperature for 4 hours with stirring and wasthen cooled to room temperature and left to stand overnight.

The next morning the reaction mixture was drowned out intoice/water/NaCl/cHCl (ratio 350 g/150 ml/12.5 g/3.5 ml) overapproximately 30-45 minutes whilst maintaining the temperature below 0°C.

The precipitate was collected by filtration and washed with an ice-coldsaturated brine solution (300 ml).

Stage II

Preparation of the Title Product

Allylamine (1.43 g, 0.025 moles) was added to a water (300 ml) andcooled to 0 to 5° C. The product obtained from stage I was added to thismixture and the pH was adjusted to the range of pH 7.8 to 8 using a 10%ammonia solution. The reaction mixture was then stirred at 0 to 5° C.for 3 hours, maintaining the pH at pH 7.8 to 8 by further additions of a10% ammonia solution. After this time the reaction mixture was warmed to40±2° C. over 45 minutes and was held at this temperature until theuptake of ammonia ceased. The reaction mixture was held at thistemperature for a further hour and then cooled to room temperatureovernight.

The pH of the reaction mixture was then adjusted to pH 1.5 to 2 usingconcentrated HCl and 20% NaCl w/v (150 g) was added. The precipitatethat formed was collected by filtration and washed with saturated brinesolution (300 ms) and then collected by filtration. The resultant pastewas added to water (600 ml), the pH was adjusted to pH 9 to 9.5 with 2MNaOH, and then dialysed versus several changes of water over the courseof 2 days. The precipitate was collected and dried in an oven at 50° C.to yield 22.76 g of the title product.

EXAMPLE 2

Preparation of:

Allylamine (0.87 g, 0.015 moles) was added to a water/ice mixture (300mls) at 0-5° C. C.I. Reactive Blue 25 (12.4 g 0.01 moles)

was then added to the mixture resulting in the pH dropping to pH2.5. ThepH of the mixture was adjusted to pH 8.3 by the addition of a 10%ammonia solution. The reaction mixture was then heated to 70-75° C. andkept at this temperature for 4 hours, maintaining the pH at pH 8.3 byfurther addition of a 10% ammonia solution. After 4 hours the reactionmixture was cooled to room temperature and the pH adjusted to pH 1.6with concentrated HCl. The resultant precipitate was collected byfiltration and washed with 10% brine (200 ml). This precipitate wastaken up in water (400 ml) and the pH was adjusted to pH 9.5 with 2MNaOH. This solution was dialysed against several changes of water andthe precipitate was collected and dried in an oven at 50° C. to yield9.57 g of the title product.

EXAMPLES 3 TO 5

Preparation of:

Compounds with varying values of x, y and z were prepared by repeatingthe procedure of Example 1 and varying the level of chlorosulphonic acidand POCl₃. Example Chlorosulphonic acid POCl₃ x y + z 3 36.5 ml, 0.54mole 8.7 ml, 0.216 mole 1 3 4   38 ml, 0.56 mole 5.3 ml, 0.131 mole 1.42.6 5 38.5 ml, 0.57 mole 1.8 ml, 0.045 mole 2 2

EXAMPLE 6

POCl₃ (9.3 g) was added, dropwise with stirring, over 15-20 minutes tochlorosulfonic acid (282 g) at room temperature. CuPc (58.8 g) was thenadded in portions over 30 min while the temperature was kept below 60°C. When all the CuPc had been added, the mixture was stirred at 40-50°C. for 10 minutes and then gradually heated to 139-140° C. and stirredfor 3 hours. The mixture was then cooled to room temperature and allowedto stand overnight. The next day the mixture was added to an ice/watermixture (1.5 L) containing 20 g of NaCl and 15 ml of c HCl. Theresultant suspension was stirred at 0° C. for 15-20 minutes and thencollected by filtration before being washed with a solution of cold 10%brine acidified to pH1 to 2 with concentrated HCl. The resultant pastewas immediately added to a solution of 2-chloroethylamine hydrochloride(70% w/w, 13.25 g) and ammonia (30% w/w solution, 4.6 g) in ice water(1.2 L) at 0-10° C. The pH was slowly adjusted to pH 7.5 with Na₂CO₃ andthen stirred at 15° C. overnight. The next day the temperature of thereacton mixture was raised to 35-40° C. and the mixture was stirred for5 hours maintaining the pH at pH8.5. The pH of the mixture was thenadjusted to pH 7 with concentrated HCl and filtered. NaCl was added tothe filtrate to 12.5% and the pH was adjusted to pH 1.5 (withconcentrated HCl) with stirring. The precipitate which formed wasfiltered and washed with 10% NaCl acidified to pH1.5 with concentratedHCl. The damp solid was dried at room temperature.

EXAMPLE 7

POCl₃ (58.3 g) was added dropwise, with stirring, over 15-20 minutes tochlorosulfonic acid (466 g) at room temperature. CuPc (58.8 g) was thenadded in portions over 30 min, keeping the temperature below 60° C. Whenall the CuPc had been added, the mixture was stirred at 60° C. for 15minutes then gradually heated to 140° C. and stirred for 3 hours. Themixture was then cooled to room temperature and allowed to standovernight. The next day the mixture was added to ice/water (1.6 L)containing 50 g of NaCl and 20 ml of c HCl. The resultant suspension wasstirred at 0° C. for 15-20 minutes and then collected by filtrationbefore being washed with a cold 3% solution of NaCl acidified to pH1 to2 with concentrated HCl. The resultant paste was slowly added to asolution of 2-chloroethylamine hydrochloride (70% w/w, 28.4 g) in icewater (1.2 L) at 0-10° C. The pH was slowly adjusted to pH 7.5 with a 6%ammonia solution and then stirred for 3 hours. The pH of the mixture wasadjusted to pH 1.5. The mixture was then stirred for 15 minutes. Theprecipitate which formed was filtered and washed with 5% NaCl adjustedto pH1.2 with concentrated HCl. The damp solid was dried at roomtemperature.

EXAMPLES 8 TO 13

Preparation of Inks 1, 3, 4, 5, 6 and 7

The compounds of Examples 1, 3, 4, 5, 6 and 7 (3.5 g) were dissolved in100 ml of a liquid medium consisting of2-pyrrolidone/thiodiglycol/Sufynol™ 465 in a weight ratio of 5:5:1 togive Inks 1 to 7 wherein Ink 1 contains the compound of Example 1, Ink 2the compound of Example 2 and so on.

Preparation of the Comparative Ink

The Comparative Ink was formed by dissolving 3.5 g of Direct Blue 199(PRO-JET™ Cyan 1 from Avecia Ltd.) (3.5 g) in 100 ml of a liquid mediumconsisting of 2-pyrrolidone/thiodiglycol/Sufynol™ 465 in a weight ratioof 5:5:1.

EXAMPLE 14

Ink-Jet Printing and Ozone Fastness

Inks 1, 3, 4, 5, 6 and 7 and the Comparative Ink were printed onto avariety of papers using a Canon 5800™ IJ printer. The printed substratewas then assessed for ozone stability using an ozone test cabinet fromHampden Test Equipment. The test was carried out for twenty four hoursat 40° C. and 50% relative humidity in the presence of 1 part permillion of ozone. Fastness of the printed ink to ozone was judged by thedifference in the optical density before and after exposure to ozoneusing a Gretag MacBeth Spectrolino. Thus, the lower the % OD loss thegreater the ozone fastness. Results are shown below in Table 2 and theseclearly demonstrate that inks based on compounds of this inventiondisplay good ozone fastness. TABLE 2 Ink Substrate % OD loss Ink 1 HPPremium Plus  1% Ink 1 SEC Premium Photo 47% Ink 3 HP Premium Plus  2%Ink 3 SEC Premium Photo 28% Ink 4 HP Premium Plus  3% Ink 4 SEC PremiumPhoto 25% Ink 5 HP Premium Plus  4% Ink 5 SEC Premium Photo 55% Ink 6 HPPremium PIus  4% Ink 6 SEC Premium Photo 37% Ink 7 HP Premium PIus −1%Ink 7 SEC Premium Photo 13% Comparative Ink HP Premium Plus  4%Comparative Ink SEC Premium Photo 63%ExamplesFurther Inks

All the inks described in Tables 1 and 11 may be prepared using thecompounds made in Examples 1 or 2 as dyes. Numbers quoted in the secondcolumn onwards refer to the number of parts of the relevant ingredientand all parts are by weight. The inks may be applied to paper by anymethod, such as thermal or piezo, of ink-jet printing. The followingabbreviations are used in Table I and II:

-   -   PG=propylene glycol    -   DEG=diethylene glycol    -   NMP=N-methylpyrollidone    -   DMK=dimethylketone    -   IPA=isopropanol    -   MEOH=methanol    -   2P=2-pyrollidone    -   MIBK=methylisobutyl ketone    -   P12=propane-1,2-diol    -   BDL=butane-2,3-diol    -   CET=cetyl ammonium bromide    -   PHO=Na₂HPO₄ and    -   TBT=tertiary butanol

TDG=thiodiglycol TABLE I Dye Na Content Water PG DEG NMP DMK NaOHStearate IPA MEOH 2P MIBK 2.0 80 5 6 4 5 3.0 90 5 5 0.2 10.0 85 3 3 3 51 2.1 91 8 1 3.1 86 5 0.2 4 5 1.1 81 9 0.5 0.5 9 2.5 60 4 15 3 3 6 10 54 5 65 20 10 2.4 75 5 4 5 6 5 4.1 80 3 5 2 10 0.3 3.2 65 5 4 6 5 4 6 55.1 96 4 10.8 90 5 5 10.0 80 2 6 2 5 1 4 1.8 80 5 15 2.6 84 11 5 3.3 802 10 2 6 12.0 90 7 0.3 3 5.4 69 2 20 2 1 3 3 6.0 91 4 5

TABLE II Dye Content Water PG DEG NMP CET TBT TDG BDL PHO 2P PI2 3.0 8015 0.2 5 9.0 90 5 1.2 5 1.5 85 5 5 0.15 5.0 0.2 2.5 90 6 4 0.12 3.1 82 48 0.3 6 0.9 85 10 5 0.2 8.0 90 5 5 0.3 4.0 70 10 4 1 4 11 2.2 75 4 10 32 6 10.0 91 6 3 9.0 76 9 7 3.0 0.95 5 5.0 78 5 11 6 5.4 86 7 7 2.1 70 55 5 0.1 0.2 0.1 5 0.1 5 2.0 90 10 2 88 10 5 78 5 12 5 8 70 2 8 15 5 1080 8 12 10 80 10

1. A compound of Formula (1) and salts thereof:

wherein: M is 2H, Si, a metal, an oxymetal group, a hydroxymetal groupor a halometal group; Pc represents a phthalocyanine nucleus of Formula(2);

R¹, R² and R³ independently are H or optionally substituted C₁₋₄alkyl;R⁴ is an optionally substituted cyclic or an optionally substitutedacyclic alkene optionally interrupted with a hetero atom; x and z areboth greater than 0; y is 0 to 4; and the sum of (x+y+z) is 2 to
 5. 2. Acompound according to claim 1 wherein M is Cu or Ni.
 3. A compoundaccording to either claim 1 or claim 2 where R⁴ is optionallysubstituted C₂₋₁₈ straight or branched chain alkylene.
 4. A compoundaccording to claim 3 where R⁴ is optionally substituted C₃₋₆ straightchain alkylene.
 5. A compound according to either claim 1 or 2 where R⁴is an optionally substituted C₂₋₁₈ straight or branched chain alkyleneinterrupted with NH.
 6. A compound according to claim 1 or claim 2 whereR⁴ is (CH₂)_(n)NH(CH₂)_(p)CH═CH(CH₂)_(q)H wherein n is 1 to 3, and p andq are each independently 0 or
 1. 7. A compound according to claim 1 orclaim 2 wherein the sum of (x+y+z) is 3 to
 4. 8. A compositioncomprising a compound as described in claim 1 and a liquid medium.
 9. Acomposition according to claim 8 wherein the liquid medium compriseswater, a mixture of water and organic solvent or organic solvent freefrom water.
 10. A composition according to either claim 8 or claim 9that is an ink suitable for use in an ink-jet printer.
 11. A process forforming an image on a substrate comprising applying an ink according toclaim 10 of the invention thereto by means of an ink-jet printer.
 12. Asubstrate printed with a compound according to claim 1, a compositionaccording to claim 8 or by means of a process according to claim
 11. 13.An ink-jet printer cartridge comprising a chamber and an ink wherein theink is in the chamber and the ink is as described in claim 10.